1. Field of the Invention
This invention concerns composites of substrate material and, applied on it, a barrier film with a barrier effect to gases and water vapor. The invention also concerns a method for producing these composites. Such composites can be used in packaging, for example, in the form of foils, panels or shapes and hollow parts, and also for technical applications, for example, as membranes or protective films for sensors.
2. Summary of Related Art
Presently, metals, e.g., aluminum or tinplate, glass, polymers, e.g., EVOH or PVDC, and polymers provided with vaporized thin metallic or oxidic films or combinations thereof are generally employed as barrier materials. As against glass and metals, polymers are characterized by their low weight and the small amounts of material needed, for which reason they are frequently used especially in the packaging field. On the other hand, due to their structure and associated permeability to gases and water vapor, polymers are unsuited for applications involving especially high requirements as to barrier properties. Gaining increasingly in significance, especially due to ecological concerns, are the renewable or recycleable polymers. However, they display a comparatively high permeability to gas and present extremely insufficient barrier properties to water vapor. Therefore, they are barred from many applications.
Owing to the mostly insufficient barrier effect to gases and water vapor, polymers are often used in combination with other materials. For example, the barrier properties of polymers allow considerable improvement by application of thin films of aluminum, aluminum oxide or silicon oxide, but the permeation rates continue to be excessively high for many applications and can be detected using conventional measuring techniques (oxygen permeability  greater than 0.5 dm3/(m2 d bar)). Moreover, renewable polymers show also after coating, as compared to coated standard polymers such as polyethylene or poly-propylene, permeation rates that are higher by far. Vaporized films being very sensitive to mechanical stresses, it is mostly necessary to laminate the coated substrates, for example with a foil.
For some time it has been known (e.g., DE-OS 38 28 098 Al) to produce scratchproof coating materials by hydrolytic polycondensation of an organofunctional silane, for example with an aluminum compound, and, as the case may be, with inorganic oxide components. Hybrid polymers (so called ORMOCERs) synthesized in this fashion possess both inorganic and organic network structures. The inorganic siliceous network structure is obtained by the sol-gel process (e.g., C. J. Brinker, D. W. Scherer, Sol-Gel-Science; The Physics and Chemistry of Sol-Gel Processing, Academic Press, Inc., New York, 1989) via controlled hydrolysis and condensation of alkoxy silanes. The siliceous network allows specific modification by including additionally metal alkoxides in the sol-gel process. Additionally, an organic network is produced by polymerization of organofunctional groups that are introduced in the material by the organoalkoxy silanes. Reactive methacrylate, epoxy or vinyl groups are polymerized by thermal or photochemical induction. The ORMOCERs produced in this way can be applied on the medium to be coated by means of conventional application techniques (spraying, brushing, etc.). Despite suitable wetting behavior and sound film adhesion, even a composite of an ORMOCER film and a polymer foil is unable to reduce the high permeability of many polymers, and notably renewable polymers, to a degree that would be required, e.g., in foodstuff packaging.
Therefore, the objective underlying the present invention is to coat substrate materials to the effect that they become extensively impermeable to gases and water vapor.
This objective is satisfied according to the invention by composites with the characterizing features set forth in claim 1 and, in process-related respects, in claim 21. Favorable embodiments and improvements of inventional composites derive from the subclaims.
A composite based on a substrate material on which in accordance with claim 1 at least two-films are arranged of which at least one barrier film contains inorganic-organic hybrid polymers (ORMOCER film) while at least one further film of substrate material or other barrier material has in comparison with the original substrate material or with single-coated substrate material a far lower permeability.
Inventional composites have a high barrier effect to gases and water vapor. Surprisingly, even the permeation rates of native polymers notably allow reduction to an extent such that these prove to be extensively impermeable to gases and water vapor, thus opening new areas of application to native polymers.
When applying an ORMOCER film 1 xcexcm to 15 xcexcm thick on a substrate material coated with a barrier film containing a metal and/or metal oxide and/or semiconductor, also the mechanical stability of the films applied first can be drastically improved, in addition to the barrier effect of the composite. Thus, the ORMOCER film assumes at the same time the function of a mechanical protective film that may make further process steps, such as lacquering or laminating, superfluous. For this reason it will mostly prove suitable to apply the ORMOCER film as the concluding film on the substrate material that has already been coated otherwise.
Of course, it is also possible to apply an ORMOCER film directly on the substrate material. Thereafter, further barrier films (for example a silicon oxide film) and/or a further substrate material film may be applied. For example, the silicon oxide sides of two coated substrate materials or the silicon oxide side of a coated and an uncoated substrate material can be combined on a conventional laminating system with ORMOCER as laminating adhesive.
Surprisingly, however, already a composite of two substrate materials, for example polymer foils with an ORMOCER barrier film arranged in between, also possess outstanding barrier properties. The ORMOCER film may also in this case serve as a laminating adhesive.
While the barrier properties of polymers are by application of a barrier film of silicon oxide of 100 nm thickness improved by a factor of 100, on average, the barrier properties of this composite increase after the additional application and curing of an ORMOCER film, surprisingly, once again by a factor of 100. This fact shows which significance attaches exactly to a double-film application.
Instead of the silicon oxide film, also metal films may be used, for example films of aluminum or other prior-art coating metals and/or semiconductor films such as silicon film and/or metal oxide films such as aluminum oxides, magnesium oxides, cerium oxides, hafnium oxides, tantalum oxides, titanium oxides such as titanium dioxide, titanium (3) oxide or titanium monoxide, yttrium oxides or zirconium oxides such as zirconium monoxide, as well as barrier-films containing mixtures of these substances. The metal and/or metal oxide and/or semiconductor films typically have a thickness of 5 nm to 1000 nm, preferably between 20 and 150 nm.
All of the polymers (e.g., polyamide, polyethylene, polyproylene or polyester) lend themselves as substrate materials for coatings according to the invention. Especially applicable as substrate materials are biologically decomposable polymers and particularly native polymers (cellophane, proteinaceous or starchy polymers) with an inherently low barrier effect. Also paper, cardboard, coated paper or coated cardboard are suited as substrate materials. Particularly pronounced improvements in view of gas and water vapor permeability are achievable with the inventional coating in the case of thin substrate mainly (for example foils) having thicknesses in the range of about 5 xcexcm to 2 mm. In addition to foils, however, also panels, shapes, hollow articles, membranes or protective films for sensors are suited as substrate materials.
Sealability of the composites can be guaranteed with the use of sealable substrate films or by application of sealable films on the composites. An example would be a copolymer film coextruded on polypropylene. Sealability is of great significance especially in foodstuff packaging. Also the use of oriented polymers, for example axially or biaxially oriented polypropylene, has proved to be favorable.
Inventionally coated plastics, notably native polymers, open for themselves a great many new areas of application which so far were unavailable to plastics (for example foodstuff preserves). Metal or glass could in many areas be substituted by plastics coated in this fashion, which means drastic weight savings. Furthermore, plastics coated in this fashion allow the manufacture of barrier materials which, unlike metals, are transparent. Possible also is the realization of a sealable, nearly varietally pure barrier composite (refer to exemplary embodiment 5).
The barrier properties of the ORMOCER allow specific adjustment by kind and share of the organic and inorganic network as well as via the network converters. Both the wetting behavior and film adhesion as well as the barrier properties can be optimized in this way. The thickness of the applied ORMOCER film ranges typically from 1 xcexcm to 15 xcexcm. The invention covers all of the ORMOCERS in the prior art. German patent publications DE-OS 38 28 098 as well as DE 43 03 570 are hereby incorporated by reference as if set forth in their entirety herein.
The further, inventional addition of functionalized SiO2 particles, which in the ORMOCER synthesis are worked in and covalently bound to the organic network, leads to a higher density of the inorganic network. Instead of SiO2 particles, also other particles may be used, for example functionalized Al2O3 particles. The barrier properties of the composite allow in this way still further improvement.
Inventional composites with barrier properties can be produced by applying at least two films on a substrate material, with at least one of these films being a barrier film containing ORMOCERs, which film is applied by brushing, spraying, rolling, centrifugal or doctor processes and subsequently cured by heat and/or photochemical induction and/or thermal induction, and with at least one further film of another barrier material or substrate material being applied before or after application of the at least one ORMOCER film.